Disazo compounds containing a quaternary ammonium group



United States Patent Ofiiice 2,945,849, Patented July 19, 1960 DISAZO COMPOUNDS CONTAINING A QUATER- NARY AMlVIONIUM GROUP Winfried Kruckenberg, Leverkusen-Bayerwerk, and K011- rad Weis, Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Mar. 3, 1958, Ser. No. 718,488 Claims priority, application Germany Mar. 4, 1957 5 Claims. (Cl. 260-185) The present invention relates to a process and to compositions for the dyeing and printing of polymers and co-polymers of acrylonitrile; more particularly it relates to a process for dyeing and printing articles comprising acrylonitrile with polyazo dyestufis containing at least one externally linked amino or ammonium group. The invention further relates to new polyazo dyestuffs.

In accordance with the invention it has been found that polyazo dyestuifs which are free of sulfonic acid and carboxylic acid groups and contain at least one externally linked basic primary, secondary or tertiary amino or quaternary ammonium group may advantageously he used for dyeing and printing articles comprising acrylonitrile.

As articles comprising acrylonitrile polymers there may be mentioned fibres, filaments, fabrics, moulded articles and the like. Also acrylonitrile co-polymers containing at least 85% by weight of acrylonitrile can be dyed and printed according to the invention.

It is an object of this invention to provide a process for dyeing and printing articles prepared from acrylonitrile polymers containing at least 85% by weight of acrylonitrile. A further object is the provision of dyed acrylonitrile polymers and co-polymers, the dyeings obtained being distinguished by good fastness properties.

The polyazo, especially disand trisazo dyestuffs to be used according to the present dyeing and printing process may belong, for example, to the benzene-azobenzene-azo-benzene series, the 'benzene-azo-naphthalene-azo-benzene series, to the naphthalene-azo-benzeneazo-benzene series or the aryl-azo-aryl-azo-arylpyrazolone, aryl-azo-aryl-azo-arylacetic acid aryland alkylamide or to the heterocyclic series. They are obtainable by usual methods by coupling of diazotized diamines or amino-azo dyestuffs with azo components. The externally linked basic group may thereby be contained in the diazo or in the azo component. Quaternary ammonium groups may be introduced into the dyestutl molecule before or after the coupling reaction by the usual reaction of tertiary amino groups with alkylating agents.

By the term externally linked amino groups we understand amino groups which are not attached to an aromatic or heterocyclic nucleus but are attached to a terminal (external) radical of the dyestutf molecules.

It is also possible to use dyestuffs containing more than one externally linked basic amino group in the molecule. On the'other hand, two dyestuffs may also contain a common, preferably quaternary, external basic group. In this way there are obtainable for example 2 dyestuft mixtures of uniform afiinity whereby at least one of the both components must be an azo dyestulf. In addition to these groups, the dyestuffs may also contain other substituents usual in azo chemistry, with the exception of sulfonic acid and carboxylic acid groups.

The monoazo dyestuffs having an externally linked primary, secondary or tertiary amino group used according to the present process are readily soluble in water in the form of their salts or as quaternary ammonium bases. The majority show a good afiinity on polyacrylonitrile fibers, even if the corresponding dyestuffs without the primary, secondary or tertiary amino group or quaternary ammonium group do not or only slightly draw on to the fibre.

The dyestuffs are dyed or printed onto the polyacrylonitrile fibre in usual manner, for example from an acid solution. The dyeings or prints thus obtained distinguish themselves by good fastness properties.

The following examples are given for the purpose of illustrating the invention, without, however, limiting it thereto.

Example 1 After the addition soda lye at 0 C. the solution is brought to a pH value of 3.5 and the precipitated dyestuif filtered with suction and dried. It dyes polyacrylonitrile fibre in fast yellowish red shades.

Example 2 In a dyebath containing 1 percent calculated on the weight of the fibre of the dyestufi of the following formula:

z s I N=N N CHsSOF J) 2Ha-N(CH:)a

CH: a

obtained by coupling 1 mol of diazotized 1-amino-4-nitrobenzcne with 1 mol of 1-amino-2,5-dimethoxybenzene, diazotizing and further coupling with 1 mol of the methyl-sulfate of l-methyl-3-N-ethyl-N-fi-trimethylammonium-ethyl-aminobenzene, 5 g. of polyacrylonitrile fibre are dyed without any further addition using a liquor-to-goods ratio of 40:1. The material is introduced at 40-50 C., the bath is brought to the boil within 20-30 minutes and the material boiled for 1 hour. The material is then rinsed and dried. A cur-rant shade is thus obtained of good fastness to wetting, particularly good fastness to subliming and ironing, and very good fastness to light.

Example 3 vinyl chloride or as.-dicyan-ethylene can be dyed in the In a dyebath containing 1 percent of a dyestuff of the same manner whereby similar shades having good fastfollowing composition: ness properties are obtained.

C5115 C N=N- N=N N\ censor- I elm-13mm). CHa CH3 CH1 calculated on the weight of the fibre, 3 g. of polyacrylo- Example 4 nitrile fibre are dyed with the addition of 3 percent of I d b th d acetic acid (referred to the wclght of the dyeing man a ye a contalmng 1 Percent Of yestuff of the following composition:

ON= OumwQq/ omsor calculated on the weight of the fibre, 5 g. of polyacryloterial) using a liquor-to-goods ratio of 4011- The manitrile fibre are dyed with the addition of 2 percent of terial is introduced at 40-50 C., the bath brought to 20 sodium carbonate (referred to the weight of the dyeing the boil within 20-30 minutes and the material boiled material) using a liquor-to-goods ratio of 40:1. The for one hour. It is then rinsed and dried. An orange material is introduced at 40-50 C., the bath brought to shade is thus obtained. the boil within 20-30 minutes and the material boiled for Instead of acetic acid there can also be used formic one hour. It is then rinsed and dried. An orange shade acid, sulfuric acid, hydrohalic acid, phosphoric acid etc. 25 is thus obtained.

Polymers of acrylonitrile containing 1 to 10% of acrylic Valuable dyeings on polyarcylonitrile fibres are also acid methyl ester or methacrylic acid methyl ester or obtained with the dyestuffs listed in the following table:

Shade of dyeing or Dyestufl print on polyacrylonltrlle fibres OCH:

/C:Hs H 0 N=N N: N\ CHISOA' reddish bordo.

Q Cam-M01 2): N CH5 H;

Cl OCHa /C1Hs O N N= N=N N\ 11x 1 current.

Q l- H OI 1 OH;

H5C1\ /CIH! /NQN=N-C NHON=N N\ (CHxSOF): reddish bordo. ccHmiI-Htc (Cami-01H. OH:

CH: H5C|\ N =N N=N CH: yellowish red. 1H: (CH3) :NH4C:

H2 N=N N\ (CHzSOt):

elm-m m) H:

OCH; 1 c,m 5 0m N= N=N-QN cmsov yellowish \C H INCH) brown. N CH: 2

OCH: 9 H;CQ'N=NC N=N mzcim-l rtonm omsor dark r y.

31 oom :N-C N=N N=N NEC:H4 I I(CHI)1 omsor grey.

01 OH; HO

OCH: 5 I /C:H5 f zN N= N=N N GEBOF yellowish \C H imam) brown. N on! on. a J

Shade of dyeing or Dyestufl print on polyacrylonitrlle fibres Cl OCH] OCH: V I aH4 H k om N=N N=N N\ /CH: 01- reddish violet mm-fi-mmon l CHI HI 0011. I l a a -C N\ omsor Do.

4' w r z ra)| 5 J v t N CHaSOF violet. V V i 1 V :Hr-N( a)a CH: V

OCH: (31H;

N omsor horde.

' aHr-Nw ah C I OCH;

l aHn cmsor yellowish dark Q brown. O H-N(CH:)F

OOH;

(QNW OI N =N N CH H, .1 1 I l OF bluish brick ted.

yellowish orange.

reddish bordo:

orapge;

m sse Example5 HO- I I=N CH:

N-CHr-CHrC Hr-NHO C OH /CH| CONHCHg-CHi-CHPN CHI is dissolved in the form of the salt of chloracetic acid in 3 litres of water to give a clear solution and then treated with 3 g. of 30 percent acetic acid. 100 grams of'poly- 20 into the dyebath at C" the bath is brought to acrylonitrile fibre are then introduced into the dyebath at 40-50- C., the bath is brought to 100'C. within 40 minutes and the material boiled for one hour. A bordored dyeing is-thus obtained.

Example 6 1 gram of the dyestufi of the formula:

c1 OOH:

is dissolved in the form of the salt of oxalic acid in 3 litres of water to give a clear solution and treated with 3 g. of 30 percent acetic acid and 2 percent sodium acetate. 100 grams of polyacrylonitrile fibre are then introduced C. within 40 minutes and the iriaterial boiled for one hour. A bluish grey dyeing is thus obtained.

Instead of the salt of oxalic acid there canbe used with similar result the sulfuric acid salt, a hydrohalic acid salt and the phosphorus acid salt.

In a similar manner there are obtained with the dyestufis of the: following table'dyeings of good fastness properties on polyacrylonitrile' fibres.

'Shade 0! dyeing or. Dyestufi prlnton polyacrylonltrlle fibres I OaN-QN: Q0011. y brown.

or N I i ll N /CHt CONHCHr-GHr-CHr-N\ CH: H10 7. cm N-omfl-oHr-oHPNHco on 31 no (l3ONHOH:G Hr-CH;N m0 i =N N=N V s r bluish bordo.

oon. no (EONH-CHr-CHFCHPNHOHO (MN-ON: QN=N brown.

i on:

Joni OgN-O-N: -QN=N NH-OOCH1 -N(GH|)1 horde.

f OH: H0

n Dom H0 CONH MNQN=NQN=N uni-mom), reddish grey.

Shade of dyeing or print on polyacrylonitrlle fibres NIH-0? (I311 (CHahN v ,3 i A 7 no CONE Example 7 16.3 parts by weight of 2-cyano-4mitro-1-aminobenzene are introduced below 20 C. into 120 parts by weight of thus obtained is then poured on ice and the clear diazo salt solution combined with a water/methanol solution of 28 parts by weight of the chloride of S-hydroxy-l-fi-trimethyl-ammonium-ethyl-aminonaphthalin. After a short 15 then neutralized to a pH 6 and combined with a solution of the diazo compound obtained from 19.6 parts by weight of 1-amino-2-triflu0ro-methyl-4-chlorobenzene.' The dyestufi thus formed precipitates. It is filtered with suction and dried. It dyes polyacrylonitrile 'fibre from weakly acid bath in bluish-green shades of good fastness properties.

Further dyestufis having similar dyeing properties are obtained in an analogous manner if using the same coupling component and the first and second diazo comtime, the dyestuif formation is complete. The solution is 25 pounds listed in the following table:

shadeordye 1 7 ing or print First diazo compound Coupling component Second diazo compound on polyaci rylonitrlle I. fabric nwnoilmt v M BR:

' LAIDiHOQA'diOYBHObBDZGIl-B.:;.l NH V 1-Amino-2,4-dicyanobenzene bluish grey.

. &IT(CHa)a]Cl- I 2 1 l-Amino-2- yano-4-nltrobenzene NH 1-Amino-2-cyano-4-nltrobenzene..;.-. greenish grey.

- I '1 1 H v 1$ oH,),]o1-

1-Amino-2eyano-5-e).1lorobenzene.... NH l-Amino-z-cyano-S-chlorobenzene violet:

H s N (C]Is):]C1'

llHz 7 Do 7: NH 1-Amin0-2-cyano-4-nitrobenzene Do.

, l-Amino-2-eyano-4-nitrobenzene 1 -Amin0-2,4-dicyano benzene greenish blue:

Shadeofdyeing or print First diazo compound Coupling component Second diazo compound on polyacrylonitrile fabric +1 N(CH!)3]C1' e i 1-Amino-2,4-dieyanobenzene NH l-Amino-iz-cyanoi-nitrobenzene reddishblue.

t riwnoilcl- I OH:

l-Amino-z-ehloro-i-nitrobenzene. NH l-Amino-Z-chloro-t-nitrobenzene grey.

suonoilor- CH: I l-Amino-2-eyeno-4-nitrobenzene..... NH fin blackbrown:

Example 8 2. The disazo dyestufi corresponding to the formula A fabric of polyacrylonitril is printed with a printing 4) paste consisting of g. of the dyestufi obtained from 2 mol of diazotized 1-amino-2-chloro-4-nitrobenzene and 1 mol of the chloride of 1-(fl-trimethyl-ammonium-ethyl)- amino-S-hydroxynaphthalene g. of thio-diglycol 30 g. cyclo hexanol 50 g. of 30 percent acetic acid 280 g. of Water 30 g. of zinc nitrate (50 percent) 30 g. of printing oil, and

50 g. of resorcinol or another phenol The print is steamed at 100 to 103 C. for 10-30 minutes and then soaped at 40-60 C. and dried. A greenishblack print of good fastness properties is thus obtained.

What we claim is:

1. A disazo dyestuff corresponding to the formula alkyl ammonium group.

3. The disazo dyestuif corresponding to the formula 4. The disazo dyestuif corresponding to the formula 5. The disazo dyestuff corresponding to the formula References Cited in the file of this patent UNITED STATES PATENTS Krzikalla et a1. Nov. 16, 1937 

1. A DISAZO DYESTUFF CORRESPONDING TO THE FORMULA 